N (thiophenalkyl) arylamines in mineral oil



Patented Aug. 8, 1950 UNITED :STATES PATENT oFmcE- N('THIOPHENALKYL) ARYLAMINES I I MINERAL OIL John H. MoCracken, Corpus Christi, 'Tex., assignor to Socony Vacuum Oil Company, Incorporated, a corporation of New York No Drawing. Application May 28, 1947, .Serialll'o. 751,124

This invention relates to a new group of chemical compounds, which compounds are useful in improving mineral oil, and to certain mineral oil compositions containing them.

'I-rior to this invention, arylamines, suchas aniline, naphthylamin es, anthranylamines, ethyl aniline, amyl aniline, and aminoethyl benzenes, as well as a number of quasi-arylamines, such as benzylamine, where the amino group isone or two carbon atoms removed from the nucleus were well known. Many of these were known to be useful addition agentsfor mineral oil, mainly for the purpose of stabilizing the oil against oxida-' foundto markedly improveits properties, particularly its stability against oxidation and discoloration. Ordinarily, the desired improvement can beaccomplished by the addition of 1% or less of. the new improving agents, but in some instances as much as is desirable."

As examples of the new class of compounds to which this-invention relates,- the following compounds have beenprepared. 1

' I Example I Chlorornethyl-thiophene was prepared by the procedure outlined by'Blicke and Burckhalter, Journal of the American Chemical Society, vol. 64;, page 47? (1942); except that the procedure was simplified by using liquid hydrochloric acid instead of gaseous hydrochloric acid.

A 3-necked flask of suitable size, fitted with a mechanical stirrer and two'dropping funnels was used for the reaction.- In it was placed 85 cc; (1

mol) ofconcentratedhydrochloric acid. The represent invention it has been naphthylamine.

action flask was cooled in an ice bath and .g.

- ture was stirred for an additional hour.

The lower layer was drawn ofi and the upper layer diluted. with an equal volume of water and extracted with ether. The extract was combined with the lower layer and the resultant product washed three times with distilled water, dried over calcium chloride, the ether distilled off, and the residue distilled under reduced pressure.

There resulted 10 g. (0.12 mol) of chloromethylthiophene boiling at 74-80 C. at 16 mm. pressure, and 5 g. of dithienylmethane boiling at 'l28 C. at 4 mm. pressure. The freshly distilled chloromethylthiophene is a water-white liquid with an odor like that of benzylchloride.

By fractionating the ether distillate and the forerun of the vacuum distillation, 11 g. (0.13 mol) of thiophene were recovered. Thus, the conversion of thiophene to chloromethylthiophone was 33%.

Solutions of 36 g. (0.26 mol) of alpha-naphthyl amine in 100 cc. of anhydrous ethyl ether and 10 g. (0.12 mol) of chlorornethylthiophene in 25 cc. of anhydrous ethyl ether were mixed and allowed to stand at room temperature for 24 hours. The precipitated naphthylamine hydrochloride was filtered off and the ether solution washed with water. After drying and distilling off the ether,

theproduct was a very dark purple oil. This.

will later be designated product A.

Product A was purified by distillation at 4 mm. pressure. A small fraction of alpha-naphthylamine boiling at -180 C. was discarded and the final product collected at 230-260 C. The product was a viscous oil, light orange in color when freshly distilled but darkening on exposure to air. Its boiling point and other characteristics clearly indicate it to be a new chemical compound and it follows logically from theoretical consideration and the characteristics of the prod uct that it was N-(2-thiophenmethyl) -alpha This purified product will later be designated product B. v

Example II V Chloromethylthiophene prepared as in ExampleI was reacted with beta-naphthylamine in the same manner as it was reacted with alphanaphthylamine in Example I. The results were substantially the same except that the product boiled at 195-2l0 C. at 1.5 mm. pressure. This 4 represent milligrams of potassium hydroxide re quired to neutralize the acids formed in a gram of oil.

product is apparently N-(2-thiophenmethyl)- N t b p hylamine. Composition Z a ot? Example III Number In a similar manner, chloromethylthiophene 011m 18.5 was reacted with aniline to produce N-(2-thio- 1O ggg ggg gg 332 phenmethyD-aniline. The product boiled at Oil A+0.l% of product of ExampleV 0.02 135-150 C. at 2-3 mm. pressure.

E p IV Example VII In a similar manner chlor0met y w Motor oils, and especially those refined by cerwas reacted with benzylamine o produce tain solvent-extraction methods tend to oxidize thiophenmelihyl)-beI1Zy1amine, the product bOiI- when submitted to high temperatures. Under ing at 5 at 5 pressurethese conditions, they tend to form products Example V which arecorrosive to metal bearings. This corrosive action may be quite severe with certain One of the corresponding di-s ubstituted com types of bearings, such as those having the Pounds W Framed by reactmg one rosionsusceptibility of cadmium-silver alloys, and N (z'thlophenmethyl) alpha naphthylamme may cause their failure within a relatively short prepared according to Example I with one mol of period of time chloromethylthiophene in ether solution. The The following test was used to determine the resultant compound was apparently corrosive action of a motor oil on an automobile thiophenmethyl) alpha naphthylamine. This connecting rod bearing. Oil D consisted of compound was a glassy, waxy mass which wa Pennsylvania neutral and residuum stocks sepaleft after distilling out unreacted materials up rat-81y refined by means of chlorex and then to -3 5 f It had Sulphur 3Q blended to give an A. S. E. 20 motor oil. The oil content of 17.8% as against a calculated sulphur was tested by adding a Section of a bearing Com contemifor the pure compgund of 192% but this taining a cadmium-silver alloy surface and was doubtless due to the presence of a certain weighing about 6 and heating it to for r f f 0f the monmsubstituted Compound, 22 hours while a stream of air was bubbled an lmpuflty compound dlmcult to against the surface of the bearing. The loss in purify due t0 high molecular welght' Weight of the bearing during this treatment The'new compounds have, among other things, measures the amount of corrosion which has been tested for effectiveness as addition agents taken p1ace The following results were to mineral oils in percentages ranging from 0.05 tamed; to 0.2% and the mineral oil compositions show 40 definite improvement as to color and neutralization number under test. This improvement is Lqssin especially marked when compounds of this series Composition $35 5 5? are used which contain a naphthalene nucleus to which is directly attached a nitrogen atom substituted' by one or more alkylthiophene radicals. 1 The following are examples of mineral oils 8% +02% OipmductAotEXampleI stabilized by the addition of various of the new 0111]) ofpl'oductAofExamplel 0 compounds. The oils used in'the following ex- 81-11 +0'05% ofpmductAofExample m l Were; l D 0.05% of product 13 of Example I 0 Oil 1 .2 Example VIII 5 0 Oil B was a distillate from a Rodessa crude which was refined with furiural, dewaxed and 69 310 M71 55 filtered. This oil wasof the type suitable for use fig in turbines. The oil was tested by bubbling 0.3 T 435 01872 liters of oxygen per hour through 25 milliliter I 7 samples of the oil in the presence of copper and Example VI iron spirals. 5 milliliters of water were added a -to each sample which were kept at a temperature 011 A is a h1ghly refined 011 suitable for use in of Q A reflux condenser was provided fo transformers. This oil was prepared by treating each sample in Omar to avoid loss of Water The 2. Coastal distillate With 40 pounds of 98% sulfollowing results were Obtained; phuric acid and 180 pounds of 103% oleum, per barrel. This was followed by washing and perco- 5 lating through clay. This type of oil tends to 001 f Nellimll form acidic products on oxidation. The oil was Composition Hours (Lwibmd) it? tested by heating samples to 120 C. and bubbling oxygen through them for '70 hours. The oxida- 2 223 0,6 tion was then determined by titrating with an Pmduct A alcoholic solution of potassium hydroxide. The 3 $32 2 13 813% data obtained for the oil alone and for the oil 3- B 2376 25 blends containing typical reaction products con- 335 0-8 0.02 templated herein are set forth in the following D0 liters per hour.

Ewample IX Oil C was a mixed Mid-Continent and Coastal distillate that had been refined by treatment with '70 pounds of 98% sulphuric acid per barrel. After the acid treatment the oil was neutralized, washed and percolated through clay. Oil C and Oil B were tested by the Brown-Boveri turbine oil test method which involves heating a test sample of the oil in the presence of a piece of copper foil at a temperature of 110 C. in air, for 72 hours, after which the color and Neutralization Number are determined. These are indicative of the extent to which the oil is afiected by oxidation. The following results were obtained:

Oil B and Oil C were also tested by the following method which is used to evaluate oils for use in turbines.

This method consists of placing 25 milliliters of the oil in each of several 150 x 25 millimeter test tubes. Each of the tubes is then covered with a glass lid and provided with a 5 millimeter delivery tube extending to the bottom of the tube.

About one gram of iron nails and a copper foil are then added to each tube. During the test, the temperature is maintained at 91 C. and clean, dry air is bubbled through the oil at a rate of 5 Every 24 hours 2 milliliters of distilled water are added to each tube. Samples are recovered from each test tube at varying periods of time and are examined for acidity (neutralization number) and color. The following results were obtained:

Neutraliz- Color Composition Hours (Lovlbond) Neliltgger Oil B 166 50 8.3 Oil B+0.2% of Product A of Example I 164 0. 8 0. 02 Do 474 8 0. 02 Oil B+0.1% of Product B of Example I 960 1. 6 0.02 Oil B +05% of Product B of Example I 330 1 0.02 Do. 720 2. 3 0. 04 D 1122 6 0.02 Oil B+0.05% of the product of ExampleI I 160 20 4. 7 Do 210 17 7.0 240 110 2. D0 336 400 16. 0 Oil C+0.2% of Product A of Example I 332 75 2. 4 Do 408 80 3. 7 Oil O+0.1% of Product 13 of Example I 331 0. l o 956 115 4. 5 Oil 0 162 19 1.0 Do 312 62 3. 0 Oil C+0.l% f Product B of Example I 168 3 0. 2 D0 331 20 0. 1

It is within the scope of this invention to add or on 6 to any lubricating composition, a suflicient proportion of any one, or any mixture of, the reaction products of this invention, to improve the characteristics thereof in any desired respect in which the reaction products are capable of improving them.

The basic lubricant in such a composition is preferably a petroleum lubricating oil of the general type commonly used in internal combustion engines and turbines. It is within the scope of this invention, however, to improve, in a similar manner, lubricants ranging all the Way from gasoline and kerosene to heavy gear lubricants, petrolatum jelly and petroleum wax. S-uch lubricants may be derived from petroleum, or any other animal, mineral or vegetable source, or may be made synthetically.

It is also within the scope of this invention to prepare and market the reaction products of this invention per se, or in the form of oil concentrates containing percentages as high as 50% of the reaction products of this invention.

It is still further within the scope of this invention to incorporate either in the lubricating compositions or in the oil concentrates, other improving agents which function to improve the oils, or concentrates, in the same or other respects than those effected by the reaction products of this invention.

What is claimed is:

1. A mineral oil containing from about 1% to about 10% of a product resulting from the reaction involving from about 0.5 to about 1 molecular portion of a haloalkylthiophene in which the alkyl radical contains from about 1 to about 4 carbon atoms per radical and a single molecular portion of a compound selected from the group consisting of primary and secondary aryl amines and amines in which the amino radical is from 1 to 2 carbon atoms removed from an aryl radical, the temperature of the reaction being maintained at about room temperature.

2. A mineral oil containing from about 1% to about 10% of N-(Z-thiophenmethyl)-a1pha naphthylamine.

3. A mineral oil containing from about 1% to about 10% of N.N-bis(2-thiophenmethyl) -alphanaphthylamine.

4. A mineral oil containing from about 1% to about 10% of N-(2-thiophenmethyl)-beta-naphthylamine.

5. A mineral oil containing from about 1% to about 10% of N-(Z-thiophenmethyl)-aniline.

6. A mineral oil containing from about 1% to about 10% of N-(2-thiophenmethyl) -benzylamine.

JOHN H. MCCRACKEN.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,140,545 Pier Dec. 20, 1938 2,154,096 Loane Apr. 11, 1939 2,160,293 Shoemaker May 30, 1939 2,367,702 Van Zoeren Jan. 23, 1945 

1. A MINERAL OIL CONTAINING FROM ABUT 1% TO ABOUT 10% OF A PRODUCT RESULTING FROM THE REACTION INVOLVING FROM ABOUT 0.5 TO ABOUT 1 MOLECULAR PORTIONOF HALOALKYLTHIOPHENE IN WHICH THE ALKYL RADICAL CONTAINS FROM ABOUT 1 TO ABOUT 4 CARBON ATOMS PER RADICAL AND A SINGLE MOLECULAR PORTION OF A COMPOUND SELECTED FROM THE GROUP CONSISTING OF PRIMARY AND SECONDARY ARYL AMINES AND AMINES IN WHICH THE AMINO RADICAL IS FROM 1 TO 2 CARBON ATOMS REMOVED FROM AN ARYL RADICAL, THE TEMPERATURE OF THE REACTION BEING MAINTAINED AT ABOUT ROOM TEMPERATURE. 